ES2783798T3 - Polyisocyanate modified with sulfamic acid, procedure for its preparation and use - Google Patents

Abstract

Sulfamic acid modified polyisocyanate, which is prepared by a reaction of polyisocyanate and sulfamic acid with the formula of ** (See formula) **, where, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R2 is butyl; or R1 is one of methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, 2-dimethyl adamantyl and 3,5-dimethyl adamantyl -1-adamantyl, R2 is propyl; or R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, and 3,5-2-norcamfanyl -dimethyl-1-adamantyl, R2 is isobutyl; preferably, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, and cycloheptyl, R2 is butyl; or R1 is methylcyclohexyl, p-methylcyclohexyl and 3,3,5-trimethylcyclohexyl, R2 is propyl; or R1 is cyclohexyl and methylcyclohexyl, R2 is isobutyl: the amount of said sulfamic acid is 0.5-20% by weight, preferably 1-10% by weight of the total weight of the polyisocyanate and sulfamic acid.

Description

DESCRIPTION

Polyisocyanate modified with sulfamic acid, procedure for its preparation and use

SECTOR OF THE INVENTION

The present invention relates to modified polyisocyanates and a mixture thereof, to the process for their preparation and to their use in the production of polyurethanes, especially their use as crosslinking components in the field of coatings and aqueous adhesives that they comprise groups capable of reacting with isocyanate groups.

STATE OF THE PRIOR ART

Recently, with the increasing attention towards environmental protection, water dispersible polyisocyanates have been used more and more in every sector because they are environmentally friendly. First, they can be used as crosslinking agents to prepare aqueous two-component coatings with good properties; secondly, they can be used in aqueous dispersion adhesives as additives; in addition, they can be used to cross-link other aqueous dispersions in textile finishing and printing, and can be used as aids for paper wetting treatment.

At present, water dispersible modified polyisocyanates can be broadly divided into two categories: nonionically modified polyisocyanates and ionically modified polyisocyanates. Nonionically modified polyisocyanates mainly use polyethers as raw materials for modification. Although polyether-modified polyisocyanates have been widely accepted on the market, they still have many shortcomings: for example, a large number of polyethers must be used to provide the polyisocyanates with good dispersion in water, which significantly lowers the concentration of isocyanates in the polyisocyanate system; second, the aid of a large shear force is required for the modified polyisocyanates to completely disperse in water; in addition, a huge amount of polyethers will be present in the solidified coating films, which will influence the water resistance of the coating films permanently.

To solve these problems, hydrophilic modifications of polyisocyanates have been achieved by the addition of hydrophilic ionic groups in polyisocyanates, and have been widely successful.

In patents EP0443138A and EP0548669A, a process for introducing carboxy groups to modify polyisocyanates is disclosed. When the carboxy groups are neutralized, the modified polyisocyanates can be easily dispersed in water without great shear force. But the shortcomings are that carboxylic acid modified polyisocyanates cannot be dispersed in the system with a pH lower than 5; furthermore, ions formed after neutralization by tertiary amines are good catalysts for the autopolymerization of isocyanates, which will result in decreased storage stability of modified polyisocyanates. Therefore, carboxy-modified polyisocyanates can only be stored in non-neutralized forms, and will be neutralized before use, which is difficult and tedious to operate.

In Patent CN101754990A, a process of using 4-aminotoluene-2-sulfonic acid to modify polyisocyanates is disclosed, said modified polyisocyanates can be dissolved in water very easily after neutralization. However, in such a process it is required to use a certain amount of polyethers, which results in a decrease in the water resistance of the coating films; furthermore, the sulfonic acids used comprise a benzene ring, which results in a decrease in the yellowing resistance properties of the coatings.

In DE4433929A, a preparation of sulfonic acid-modified polyisocyanates using small molecular sulfonic acid (2-hydroxypropanesulfonic acid) and large molecular sulfonic acid (hydroxyl terminated polyethersulfonic acid) is disclosed, such as the products of the Tegomer series) that, after ionization, said modified polyisocyanates can be well dispersed in water. However, the 2-hydroxypropanesulfonic acid used herein is carcinogenic, and special large molecular size sulfonates are generally provided in industry in the form of sodium salts, and since a sulfonic acid neutralized by a strong base it is poorly compatible with the other component in the two-component coating, resulting in a two-component opaque system and an inhomogeneous coating. And the sodium ion will remain in the coating films and influence the water resistance of the coating films permanently.

In Patent CN1190450C, the modified polyisocyanates are prepared using 3- (cyclohexylamino) -propanesulfonic acid and 2- (cyclohexylamino) -ethanesulfonic acid, the modified polyisocyanates obtained can be dispersed in water homogeneously without high shear force, and the Sulfonate-modified polyisocyanates neutralized by tertiary amines have very good stability in storage. However, the reaction time of the preparation of polyisocyanates modified with sulfamic acids of the process of said patent is long, the types of sulfamic acids that can be used to carry out the hydrophilic modifications of the polyisocyanates through a reaction of this type are very limited, only 3- (cyclohexylamino) -propanesulfonic acid and 2- (cyclohexylamino) -ethanesulfonic acid are described, and it is explicitly mentioned that many other sulfamic acids with very similar structures cannot react with polyisocyanates, even under more drastic conditions .

CHARACTERISTICS OF THE INVENTION

One of the objectives of the present invention is to provide a cycloalkyl substituted sulfamic acid modified polyisocyanate, said sulfamic acid modified polyisocyanate possesses advantages of good dispersion in water and adequate storage stability, the two-component coatings produced by said polyisocyanate modified with cycloalkyl substituted sulfamic acid have a long service life, and the coating films have good properties and the advantages of water resistance and acid resistance and base resistance and high gloss.

Another objective of the present invention is to provide a process for the preparation of said sulfamic acid modified polyisocyanate, and the bias mentioned in the prior art, that other sulfamic acids with similar structures, except 3- (Cyclohexylamino) -propanesulfonic acid and 2- (cyclohexylamino) -ethanesulfonic acid, cannot react with the polyisocyanate, it can be overcome by improving the process in the present invention. The process of the process is easy to operate, thus it can shorten the reaction time of sulfamic acid and polyisocyanates and the reaction conditions can be milder.

To achieve the objectives of the present invention, the present invention provides the following technical solutions:

From one aspect, the present invention provides such a sulfamic acid modified polyisocyanate, which is prepared by a reaction of polyisocyanate and sulfamic acid with the formula of

H T N- R: ---- SO, H

In the above formula, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamphanyl and 3,5-dimethyl-1-adamantyl, R2 is butyl;

or R1 is one of methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, 2-dimethyl adamantyl and 3,5-dimethyl adamantyl -1-adamantyl, R2 is propyl;

or R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, and 3.5-dimethyl-1, 2-dimethyl-adamantyl -adamantyl, R2 is isobutyl;

preferably, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, and cycloheptyl, R2 is butyl; or R1 is methylcyclohexyl, p-methylcyclohexyl and 3,3,5-trimethylcyclohexyl, R2 is propyl; or R1 is cyclohexyl and methylcyclohexyl, R2 is isobutyl.

The amount of said sulfamic acid is 0.5-20% by weight, preferably 1-10% by weight of the total weight of the polyisocyanates and sulfamic acid.

The sulfamic acid-modified polyisocyanates of the present invention possess the following characteristics:

a) the average functionality of isocyanates is at least 1.8,

b) the content of isocyanate groups is 4.0-35.0% by weight,

c) the SO3-content is 0.1-6.8% by weight,

and optionally

d) the content of ethoxy units that were attached to the polyether chain is 0-15% by weight, said polyether chain comprises an average of 5-30 ethoxy units;

preferably, the sulfamic acid-modified polyisocyanates of the present invention possess the following characteristics:

a) the average functionality of isocyanates is 2.0-4.8,

b) the content of isocyanate groups is 6.0-31.0% by weight,

c) the SO3- content is 0.2-4.8% by weight,

and optionally

d) the content of ethoxy units that were attached to the polyether chain is 4-12% by weight, said polyether chain comprises an average of 10-20 ethoxy units.

The polyisocyanate used to prepare the sulfamic acid-modified polyisocyanates of the present invention is one or more of aliphatic, alicyclic, aromatic, araliphatic, and modified polyisocyanates with an average functionality of 2.0-5.0 and a content of isocyanate groups of 7.0-32.0% by weight. One or more of aliphatic, alicyclic and modified polyisocyanates having an average functionality of 2.0-5.0, and an isocyanate group content of 12.0-25.0% by weight are preferred.

The above modified polyisocyanates were prepared by modifying at least two simple aliphatic, alicyclic, aromatic and / or araliphatic diisocyanates and comprise uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures. Specific examples can be found in the following patent documents: DE1670666A, DE1954093A, DE2414413A, DE2452532A, DE2641380A, DE3700209A, DE3900053A, DE3928503A, EP0336205A, EP0339396A and EP0798299A, etc .;

Modified polyisocyanates comprising isocyanurate groups, which are based on one or more of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 4,4'-dicyclohexylmethanediisocyanate (H12MDI), are most preferred.

Suitable diisocyanates for the preparation of the above modified polyisocyanates comprising uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures are those that can be obtained by the phosgene process or the phosgene-free process, for example by a thermal cleavage of urethane. Preferred diisocyanates are those with a molecular weight of 100-500 with isocyanate groups linked aliphatically, cycloaliphatically, araliphatically and / or aromatically, such as 1,4-butanediisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2-methyl- 1,5-pentanediisocyanate, 2,2-dimethyl-1,5-pentanediisocyanate, 2,2,4-trimethyl-1,6-hexanediisocyanate and 2,4,4-trimethyl-1,6-hexanediisocyanate, 1,10- Decandiisocyanate, 1,3-hexanediisocyanate and 1,4-hexanediisocyanate, 1,3-bis (isocyanate-methyl) -cyclohexane and 1,4-bis (isocyanate-methyl) -cyclohexane, isophorone diisocyanate (IPDI), 4,4'- dicyclohexylmethanediisocyanate (H12MDI), 1-isocyanate-1-methyl-4 (3) -isocyanate-methylcyclohexane, bis (methyloisocyanate) -norbornane, 1,3-bis (2-isocyanate-propan-2-yl) -benzene and 1, 4-bis (2-isocyanate-propan-2-yl) -benzene (TMXDI), 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate (MDI ) and 1,5-naphthalene diisocyanate or a mixture of these diisocyanates.

Furthermore, water dispersible diisocyanates (or polyisocyanates) modified with ethoxy units containing polyethers can also be used as a source of polyisocyanates.

The sulfamic acid modified polyisocyanates of the present invention can be prepared in the presence of monohydric polyether, the number average molecular weight is 300-1000, preferably 400-800, the number of ethoxy units is 5-30 preferably 10-20.

In the present invention, the starting component that can be used in the preparation of said polyether can be: a saturated monohydric alcohol, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secbutanol, isomeric pentanol, hexanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, cyclohexanol, hydroxylmethylcyclohexane, and 3-ethyl-3-hydroxylmethyloxetane; unsaturated alcohols, such as allyl alcohols, 1,1-dimethyl-allyl alcohols, or oleyl alcohol; aromatic alcohols, such as phenols, isomeric methylphenol, or methoxyphenol; araliphatic alcohols, such as benzyl alcohol, anisyl alcohol, or cinnamyl alcohol; secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methyl-cyclohexylamine and N-ethyl-cyclohexylamine or dicyclohexylamine; heterocyclic secondary amines, such as morpholine, pyrrolidine, piperidinoethyl pyrazole, etc .; a preferred starting component is a monohydric alcohol saturated with at most 4 carbons, methanol is especially preferred as the starting component.

The polymeric monomers are one or two of propylene oxide and ethylene oxide, where the amount of ethylene oxide is at least 40 mol%, preferably at least 50 mol%, based on total moles. of polymeric monomers.

The monohydric polyether is optionally used together to prepare the sulfamic acid modified polyisocyanates of the present invention. The content of ethoxy units attached to the monohydric polyether chain in the modified polyisocyanates is 0-15% by weight, preferably 4-12% by weight, based on the total weight of the polyisocyanate, sulfamic acid and polyether.

In another aspect, the present invention discloses a process for the preparation of polyisocyanates modified with sulfamic acid, said process comprises: the reaction of polyisocyanates with sulfamic acid with the formula of

H ? N ----- R; ---- SO.H

in the presence of tertiary amines.

In the above formula, Ri is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamanthyl, 2-adamanthyl and 3,5-dimethyl-1-adamantyl, R2 is butyl;

or R1 is one of methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, 2-dimethyl adamantyl and 3,5-dimethyl adamantyl -1-adamantyl, R2 is propyl;

or R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, and 3.5-dimethyl-1, 2-dimethyl-adamantyl -adamantyl, R2 is isobutyl;

preferably, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, and cycloheptyl, R2 is butyl; or R1 is one of methylcyclohexyl, p-methylcyclohexyl and 3,3,5-trimethylcyclohexyl, R2 is propyl; or R1 is one of cyclohexyl and methylcyclohexyl, R2 is isobutyl;

the amount of sulfamic acid is 0.5-20% by weight, preferably 1-10% by weight of the total weight of the polyisocyanates and sulfamic acid; Y

wherein in said reaction said polyisocyanates are applied by a two-stage addition process, in which the first part of the polyisocyanates are mixed with sulfamic acid, tertiary amine and optional polyether, subsequently, they react for 3-5 hours at 95-110 ° C, subsequently, the remaining part of polyisocyanates is added. After cooling to room temperature, sulfamic acid modified polyisocyanates are obtained; in which the first part of polyisocyanates represents 30-90% by weight, preferably 50-80% by weight of the total weight of the polyisocyanates.

Optionally, the process of the present invention is carried out in the presence of polyether comprising ethoxy units, and / or the polyisocyanate used already comprises ethoxypolyether units.

In the process of the present invention, the polyisocyanates that are used to prepare the sulfamic acid-modified polyisocyanates of the present invention are one or more of aliphatic, alicyclic, aromatic, araliphatic polyisocyanates with an average functionality of 2.0-5.0 and a content of isocyanate groups of 7.0-32.0% by weight.

One or more of the aliphatic, alicyclic and modified polyisocyanates having an average functionality of 2.0-5.0, an isocyanate group content of 12.0-25.0% by weight are preferred.

The above modified polyisocyanates can be polyisocyanates which were prepared by modifying at least two of simple aliphatic, alicyclic, aromatic and / or araliphatic diisocyanates and comprise uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and / or oxadiazine trione, Specific examples can be found in the following patent documents: DE1670666A, DE1954093A, DE2414413A, DE2452532A, DE2641380A, DE3700209A, DE3900053A, DE3928503A, EP0336205A, EP0339396A and EP0798299A, etc .;

Suitable diisocyanates for the preparation of the above modified polyisocyanates comprising uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures are those that can be obtained by the phosgene process or phosgene-free processes, for example, by a thermal cleavage of urethane. Preferred diisocyanates are those with a molecular weight of 100-500 with isocyanate groups linked aliphatically, cycloaliphatically, araliphatically and / or aromatically, such as 1,4-butanediisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2-methyl- 1,5-pentanediisocyanate, 2,2-dimethyl-1,5-pentanediisocyanate, 2,2,4-trimethyl-1,6-hexanediisocyanate and 2,4,4-trimethyl-1,6-hexanediisocyanate, 1,10- Decandiisocyanate, 1,3-hexanediisocyanate and 1,4-hexanediisocyanate, 1,3-bis (isocyanate-methyl) -cyclohexane and 1,4-bis (isocyanate-methyl) -cyclohexane, isophorone diisocyanate (IPDI), 4,4'- dicyclohexylmethanediisocyanate (H12MDI), 1-isocyanate-1-methyl-4 (3) -isocyanate-methylcyclohexane, bis (methyloisocyanate) -norbornane, 1,3-bis (2-isocyanate-propan-2-yl) -benzene and 1, 4-bis (2-isocyanate-propan-2-yl) -benzene (TMXDI), 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate (MDI ) and 1,5-naphthalene diisocyanate or a mixture of these diisocyanates.

More preferred are modified polyisocyanates containing isocyanurate groups that are based on one or more of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI).

In addition, water dispersible diisocyanates (or polyisocyanates) modified with polyethers containing ethoxy units can also be used as the source of polyisocyanates.

In the process of the present invention, said polyether is a monohydric polyether, the number average molecular weight is 300-1,000, preferably 400-800, the number of ethoxy units is 5-30, preferably 10- twenty.

The starting component that can be used in the preparation of the polyether of the process of the present invention can be: a saturated monohydric alcohol, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secbutanol, isomeric pentanol, hexanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, cyclohexanol, hydroxylmethylcyclohexane, and 3-ethyl-3-hydroxylmethyloxetane; unsaturated alcohols, such as allyl alcohols, 1,1-dimethyl-allyl alcohols, or oleyl alcohol; aromatic alcohols, such as phenols, isomeric methylphenol, or methoxyphenol; araliphatic alcohols, such as benzyl alcohol, anisyl alcohol, or cinnamyl alcohol; secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methyl- and N-ethyl-cyclohexylamine or dicyclohexylamine; heterocyclic secondary amines, such as morpholine, pyrrolidine, piperidinoethyl pyrazole, etc .;

A preferred starting component is a saturated monohydric alcohol with at most 4 carbons, methanol is especially preferred.

The polymeric monomers are one or more of propylene oxide and ethylene oxide, where the amount of ethylene oxide is at least 40 mol%, preferably at least 50 mol%, based on total moles. of polymeric monomers.

In the process of the present invention, the monohydric polyether optionally is used together to prepare the sulfamic acid-modified polyisocyanates of the present invention, the content of the ethoxy units attached to the monohydric polyether chain in the modified polyisocyanate is 0- 15% by weight, preferably 4-12% by weight, based on the total weight of the polyisocyanate, sulfamic acid, and polyether. In the process of the present invention, said tertiary amine is a non-cyclic and / or cyclic substituted aliphatic and / or alicyclic tertiary amine, comprising tertiary monoamines, such as trimethylamine, triethylamine, tripropylamine, dimethylcyclohexylamine, N-methylmorpholine, N- methylquinoline, N-ethylquinoline, etc .; or tertiary diamine, such as 1,3-bis- (dimethylamino) -propane and N, N-dimethylpiperazine, etc .; one or more of triethylamine, dimethylcyclohexylamine and N-methylmorpholine are preferred.

In the process of the present invention, the molar ratio of said tertiary amine to the SO3- group of sulfamic acid is 0.2-2.0: 1, preferably 0.5-1.5: 1.

In the process of the present invention, the molar ratio of isocyanate groups to groups that are reactive to isocyanate groups is kept at 4-300: 1, the molar ratio of isocyanate groups to groups that are groups that are reactive to isocyanate is holds at 6-200: 1.

In the process of the present invention, in one aspect, said tertiary amine is used to neutralize the sulfonic acid group in the sulfamic acid to form sulfonate, in another aspect, said tertiary amine is used as a phase transition catalyst of the reaction of polyisocyanates and sulfamic acid.

Said tertiary amine can also be used in combination with the catalysts commonly used in polyurethane chemistry, such as pyridine, methylpyridine, benzyldimethylamine, N, N-dimethylpiperazine; Organometallic catalysts: aluminum tri (ethylacetyl acetate), tin octoate, zinc octoate, 2-ethyl-1-tin (II) hexanoate, dibutyl tin (IV) dichloride, dibutyl tin (IV) diacetate, dilaurate dibutyl tin (IV), dioctyl tin (IV) diacetate or molybdenum glycolate, or any desired mixture of these catalysts. And the utilization amount of these common catalysts is 10-2,000 ppm, preferably 100-500 ppm of the total weight of the reaction material.

In the process of the present invention, in the presence of tertiary amine, polyisocyanates and sulfamic acid can be chosen to react in solvents that are inert towards isocyanate groups, such as one or a mixture of more of the solvents: acetone, butanone, cyclopentanone, ethyl acetate, butyl acetate, N-ethylpyrrolidone, N-methylpyrrolidone, toluene, xylene, chlorobenzene, propylene glycol methyl ether acetate, 1-methoxylprop-2-yl acetate, 3-methoxyl-butyl acetate, aromatics (such as Solvesso®, Isopar®, Nappar® solvent oil name), dimethyl carbonate, diethyl carbonate, butyrolactone, caprolactone and methyl caprolactone, etc.

It is revealed that, according to the process described in Patent CN1190450C, said sulfamic acid (such as cyclohexylamino butanesulfonic acid, cyclohexylmethylamino propanesulfonic acid, 4-methylcyclohexylamino propanesulfonic acid, etc.) of the present invention does not react with polyisocyanates at 80 ° C, even When the reaction temperature rises to 110 ° C, many solids remain in suspension after 10 hours of reaction. This is mainly because the difference in molecular structure between said sulfamic acid used in the present invention and cyclohexylamino propanesulfonic acid and cyclohexylamino ethanesulfonic acid, results in the decrease in the activity of the reaction. Said mentioned sulfamic acid It cannot react with polyisocyanates in the common synthesis process system. Even under more drastic conditions with increasing temperature, a large amount of suspended solids will remain. These results comply with the opinion described in Patent CN1190450C that "many other sulfamic acids with very similar structures cannot react with polyisocyanates even under more drastic conditions".

Surprisingly, in another aspect, it is revealed that, if unmodified polyisocyanates are added by a two-stage addition process, i.e. the polyisocyanates split into two parts, in which the first part reacts with the cycloalkyl substituted sulfamic acid of the present invention completely, subsequently, the remainder of the polyisocyanate is added to the mixture. The general reaction can be completed in 3-5 hours, finally transparent modified polyisocyanate which is stable for storage can be obtained. And the lower the proportion of the first part of polyisocyanates, the faster the reaction rate.

Polyisocyanates are not compatible with the sulfamic acid monomer (such as cyclohexylamino butanesulfonic acid, cyclohexylmethylamino propanesulfonic acid, 4-methylcyclohexylamino propanesulfonic acid) of the present invention. The reactants are divided into two phases in the reaction system, that is, the solid sulfamic acid monomer phase and the liquid polyisocyanate phase. In this way, the reaction is a typical heterogeneous reaction, which means a very slow reaction rate or even no reaction. Suitable phase transition catalysts make heterogeneous systems that originally have a very slow reaction rate or even have no reaction to react easily. The concentration of the catalysts (based on the total weight of the reaction materials) directly determines the reaction rate. After many studies, it is revealed that tertiary amines not only have very good compatibility with polyisocyanates, but also have some compatibility with sulphamic acid monomers, which meets the characteristics of phase transition catalysts. Therefore, the tertiary amines in the system not only play the role of neutralizing agent, but also act as phase transition catalysts. Only through the dual function of tertiary amines, the solid sulfamic acid monomer can react with the unmodified polyisocyanates in the liquid phase. Whereas, without tertiary amines, polyisocyanates do not react with the sulfamic acids of the present invention. It can be concluded that tertiary amines are not only neutralizing agents, but also phase transition catalysts. According to the present invention, the concentration of the phase transition catalysts (tertiary amines) in the first stage of the new two-stage addition process is higher than that of the common process, which results in an increased reaction rate and a shorter reaction time. The lower the proportion of polyisocyanates used in the first stage with respect to the total of polyisocyanates, the higher the concentration of the phase transition catalysts (tertiary amines) and the faster the reaction rate. Theoretically, in a common single-stage process, increasing the tertiary amine concentration simultaneously can also shorten the reaction time. But the higher the concentration of the added tertiary amine, the higher the concentration of the tertiary amine that remains in the system after the reaction is complete, which will decrease the storage stability of the modified polyisocyanates. Therefore, by the new two-stage addition process disclosed in the present invention, the barely reacting sulfamic acid monomer can react with polyisocyanates, modified polyisocyanates can be prepared that can self-emulsify in water without adding emulsifying agent. no high velocity shear forces. Furthermore, such modified polyisocyanates are easily prepared. The raw materials are not very toxic, and the neutralizing agents (phase transition catalysts) can be freely chosen, modified isocyanates are obtained which are highly compatible with common water dispersible hydroxypolyurethanes.

The cycloalkyl substituted sulfamic acids disclosed in the present invention enrich the types of sulfamic acid that can be used in the hydrophilic modification of polyisocyanates.

Furthermore, compared to the surfactant molecules formed using the reaction of sulfamic acid and polyisocyanate, disclosed in Patent CN1190450C, the surfactant molecules possess larger hydrophobic groups that were obtained by the reaction of sulfamic acid that possesses a structure larger space with polyisocyanates. This means a lower critical micellar concentration in water, better emulsification and film performance of the two-component coating applied in water-dispersible hydroxyl dispersions, and better performance of water resistance and resistance to bases. Furthermore, compared to the modified polyisocyanate prepared in Patent CN1190450C, the modified polyisocyanate prepared by the two-stage addition process in the present patent has a longer shelf life while used in a two-component coating system (approximately , 4 hours).

According to another aspect of the present invention, the present invention also provides said sulfamic acid modified polyisocyanate and the use of the modified polyisocyanates as starting components in the water-dispersible synthesized polyurethane, especially the use as crosslinking agents in coatings and two-component water dispersible adhesives.

The sulfamic acid-modified polyisocyanates obtained in the present invention are clear and colorless (or light yellow in color), possess good storage stability at room temperature and good dispersibility in water. The composition has been described above. Furthermore, said sulfamic acid modified polyisocyanates possess high average functionality and high isocyanate content. Although the SO3- concentration is low, the sulfamic acid modified polyisocyanates in the present invention still have very good dispersibility. This offers great advantages in the application of two component aqueous coatings. The two-component coatings prepared by the sulfamic acid modified isocyanate of the present invention have very good performances in solvent resistance and chemical resistance; water resistance is also excellent as a result of the low content of hydrophilic groups.

The sulfamic acid modified polyisocyanates in the present invention, as crosslinking agents or synthetic partner, can be dispersed and applied in aqueous binding agents, said binding agents comprise groups that are capable of reacting with isocyanates, especially hydroxyls.

The sulfamic acid modified polyisocyanates in the present invention are used as crosslinking components in coating binders in those amounts that correspond to an equivalent molar ratio of isocyanate groups to groups that are reactive towards isocyanate groups of 0.5-2, 5: 1.0, preferably 0.8-1.8: 1; The sulfamic acid modified polyisocyanate of the present invention can also be mixed into aqueous coating binders in small amount to obtain special properties. Finally, the present invention also discloses that sulfamic acid modified polyisocyanates can be used as a starting component to prepare dispersion of water dispersible blocked polyisocyanates or water dispersible blocked polyisocyanates.

The sulfamic acid modified polyisocyanate of the present invention can also be blocked by a blocking agent and can be used to prepare a modified polyisocyanate emulsion that can be used in one-component systems. Suitable blocking agents are, for example, diethyl malonate, ethyl acetoacetate, 3,5-dimethylpyrazole, imidazole, e-caprolactam, etc., or a mixture of these blocking agents. The sulfamic acid modified polyisocyanates of the present invention can be homogeneously dispersed in aqueous coatings or binders due to their excellent dispersibility in water, leading to coating films with excellent optical properties, especially high surface gloss, high flowability and high transparency.

The sulfamic acid-modified polyisocyanates of the present invention, except as used as crosslinking components for coatings and two-component adhesives, may also be very suitable as crosslinking agents in textile finishing, print coating binders and can be used for crosslinking other aqueous dispersions or as aids for the wetting treatment of paper. With strong mechanical stirring, stable blue emulsions can be prepared by the modified polyisocyanate blocked by blocking agents, which is made dispersible in water.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be further illustrated by the following examples, it should be noted that the examples are not limiting of the scope of protection of the present invention.

Raw Materials

Component a)

Polyisocyanate 1 (Wannate HT-100, Wanhua, Ningbo, HDI-based polyisocyanates, content of isocyanate groups 21.5-22.5% by weight, average functionality 3.3-3.8);

Polyisocyanate 2 (Bayer NZ1, polyisocyanate based on HDI and IPDI, content of isocyanate groups 20% by weight, average functionality 3.3-3.5);

Component b)

4- (Cyclohexylamino) -butanesulfonic acid: cyclohexylamine and 1,4-butylsulfone are mixed, corresponding to an equivalent molar ratio of 3: 1, with the solvent dioxane, and subsequently they react at 80 ° C for 6 h, solids are obtained by washing with acetone until they turn white (for example, see US2007010573 A1);

4- (cyclohexylmethylamino) -butanesulfonic acid: it is prepared by cyclohexanemethylamine and 1,4-butylsulfone, according to the previous procedure;

4- (p-methylcyclohexylamino) -butanesulfonic acid: it is prepared by p-methylcyclohexanoamine and 1,4-butylsulfone, according to the previous procedure;

4- (cycloheptyl) -butanesulfonic acid: it is prepared by cycloheptane and 1,4-butylsulfone, according to the previous procedure;

3- (cyclohexylmethylamino) -propanesulfonic acid: it is prepared by cyclohexylmethylamine and 1,3-propanesulfone, according to the previous procedure;

3- (p-methylcyclohexylamino) -propanesulfonic acid: it is prepared using p-methylcyclohexylamine and 1,3-propane sulfone, according to the previous procedure;

3- (3,3,5-Trimethylcyclohexylamino) -propanesulfonic acid: it is prepared by 3,3,5-trimethylcyclohexylamine and 1,3-propanesulfone, according to the previous procedure;

3- (cyclohexylamino) -2-methyl-1-propanesulfonic acid: it is prepared by cyclohexylamine and 1,3-butylsulfone, according to the previous procedure;

3- (cyclohexylmethylamino) -2-methyl-1-propanesulfonic acid: it is prepared by cyclohexylmethylamine and 1,3-butylsulfone, according to the previous procedure;

Component c)

Monohydric polyether comprising ethoxy units (GEP-105, Wan hua rong wei, molecular weight 500-600, an average hydroxyl value of 100-110 mg KOH / g, number of ethoxyl units 11-13);

Please note that the following examples are only used to attest to the present invention, but not to limit the present invention. Unless otherwise defined, all percentages refer to percentages by weight.

Example 1:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine to 133 g of polyisocyanate 1 (0.70 mol). The reaction lasted 5 h at 100 ° C. Subsequently, 57 g (0.29 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid-modified polyisocyanates are obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.3% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 5,000 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 2:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine to 95 g of polyisocyanate 1 (0.50 mol). The reaction lasted 3 hours at 100 ° C. Subsequently, 95 g (0.50 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.3% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 5,000 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 3:

In a four-necked round-bottomed flask equipped with a mechanical stirrer, a condenser tube, a thermometer, and a nitrogen inlet and outlet, 2 g (0.008 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 1, were added. 08 g (0.008 mol) of dimethylcyclohexylamine to 138 g of polyisocyanate 1 (0.73 mol). The reaction lasted 5 h at 100 ° C. Subsequently, 60 g (0.32 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 21.2% by weight

average functionality of isocyanate groups: 3.5

viscosity (25 ° C): 3,500 mPa ■ s

SO3- content: 0.33% by weight

content of ethoxy units: 0

Example 4:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 20 g (0.084 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 10, were added. 8 g (0.084 mol) of dimethylcyclohexylamine to 126 g of polyisocyanate 1 (0.69 mol). The reaction lasted 5 h at 100 ° C. Subsequently, 54 g (0.30 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 17.0% by weight

average functionality of isocyanate groups: 3.2

viscosity (25 ° C): 6,300 mPa ■ s

SO3- content: 3.23% by weight

content of ethoxy units: 0

Example 5:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine, 22.8 g (0.041 mol) of GEP-105 monohydric polyether to 133 g of polyisocyanate 1 (0.70 mol). The reaction lasted 5 h at 100 ° C. Subsequently, 57 g (0.29 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data: solid content: 100%

content of isocyanate groups: 16.6% by weight

average functionality of isocyanate groups: 3.3

viscosity (25 ° C): 5,700 mPa ■ s

SO3- content: 1.48% by weight

content of ethoxy units: 9.4% by weight

Example 6:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine, 28 g (0.050 mol) of GEP-105 monohydric polyether to 133 g of polyisocyanate 1 (0.70 mol). The reaction lasted 5 h at 100 ° C. Subsequently, 57 g (0.29 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data: solid content: 100%

content of isocyanate groups: 16.0% by weight

average functionality of isocyanate groups: 3.1

viscosity (25 ° C): 3,700 mPa ■ s

SO3- content: 1.43% by weight

content of ethoxy units: 11.3

Example 7:

In a four necked round bottom flask equipped with a mechanical stirrer, a condenser tube, a thermometer, and a nitrogen inlet and outlet, 10 g (0.084 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5 , 4 g (0.084 mol) of dimethylcyclohexylamine, 51.4 g of propylene glycol methyl ether acetate to 133 g of polyisocyanate 1 (0.90 mol). The reaction lasted 3 hours at 100 ° C. Subsequently, 57 g (0.29 mol) of polyisocyanate 1 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data:

solids content: 80%

content of isocyanate groups: 15.2% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 1,200 mPa ■ s

SO3- content: 1.32% by weight

content of ethoxy units: 0

Example 8:

In a four necked round bottom flask equipped with a mechanical stirrer, a condenser tube, a thermometer, and a nitrogen inlet and outlet, 10 g (0.084 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5 , 4 g (0.084 mol) of dimethylcyclohexylamine to 133 g of polyisocyanate 2 (0.63 mol). The reaction lasted 3 hours at 100 ° C. Subsequently, 57 g (0.27 mol) of polyisocyanate 2 were added and mixed homogeneously. After cooling to room temperature, the sulfamic acid modified polyisocyanate is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 17.6% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,800 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 9:

10 g (0.042 mol) of 3- (cyclohexylmethylamine) -propanesulfonic acid were applied to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid in Example 1, the remainder of the elements can be referred to example 1, it is obtained polyisocyanate modified with sulfamic acid with the following characteristic data: solids content: 100%

content of isocyanate groups: 19.2% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,700 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 10:

10 g (0.042 mol) of 3- (p-methylcyclohexylamino) -propanesulfonic acid were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid in Example 1, the rest of the elements can be referred to In example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data: solid content: 100%

content of isocyanate groups: 19.3% by weight

average functionality of isocyanate groups: 3.3

viscosity (25 ° C): 5,000mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 11:

10 g (0.038 mol) of 3- (3,3,5-trimethylcyclohexylamino) -propanesulfonic acid and 4.8 g (0.038 mol) of dimethylcyclohexylamine were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) acid. -butanesulfonic acid and the 5.4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.4% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,500 mPa ■ s

SO3- content: 1.44% by weight

content of ethoxy units: 0

Example 12:

10 g (0.040 mol) of 4- (p-methylcyclohexylamino) -butanesulfonic acid and 5.1 g (0.040 mol) of dimethylcyclohexylamine were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid and the 5.4 g (0.042 mol) of dimethylcyclohexylamine from example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.2% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,900 mPa ■ s

SO3- content: 1.57% by weight

content of ethoxy units: 0

Example 13:

10 g (0.040 mol) of 4- (cycloheptylamino) -butanesulfonic acid and 5.1 g (0.040 mol) of dimethylcyclohexylamine were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid and the 5, 4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.0% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,800 mPa ■ s

SO3- content: 1.57% by weight

content of ethoxy units: 0

Example 14:

10 g (0.040 mol) of 4- (cyclohexylmethylamino) -butanesulfonic acid and 5.1 g (0.040 mol) of dimethylcyclohexylamine were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid and 5.4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.4% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,700 mPa ■ s

SO3- content: 1.57% by weight

content of ethoxy units: 0

Example 15:

10 g (0.042 mol) of 3- (cyclohexylamino) -2-methyl-1-propanesulfonic acid were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid in Example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data: solids content: 100%

content of isocyanate groups: 19.2% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 5,100 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 16:

10 g (0.040 mol) of 3- (cyclohexylmethylamino) -2-methyl-1-propanesulfonic acid and 5.1 g (0.040 mol) of dimethylcyclohexylamine were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) acid. -butanesulfonic acid and the 5.4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.3% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 5,000mPa ■ s

SO3- content: 1.64% by weight

content of ethoxy units: 0

Example 17:

2.7 g (0.021 mol) of dimethylcyclohexylamine were used to replace the 5.4 g (0.042 mol) of dimethylcyclohexylamine in Example 1, and the reaction time was extended to 6 h, the rest of the elements can be referred to Example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.3% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,900 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Example 18:

8.1 g (0.063 mol) of dimethylcyclohexylamine were used to replace the 5.4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1, the polyisocyanate modified with sulfamic acid is obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.1% by weight

Average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,700 mPa ■ s

SO3- content: 1.65% by weight

content of ethoxy units: 0

Comparative example 1:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine to 190 g of polyisocyanate 1 (0.99 mol). The reaction lasted 20 hours at 80 ° C. The reaction system was cloudy, indicating that, at this temperature, 4- (cyclohexylamino) -butanesulfonic acid did not react with the polyisocyanates.

Comparative example 2:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid, 5, were added. 4 g (0.042 mol) of dimethylcyclohexylamine to 190 g of polyisocyanate 1 (0.99 mol). The reaction lasted 10 h. There was still a large amount of suspended material in the system, which means that 4- (cyclohexylamino) -butanesulfonic acid had hardly reacted with the polyisocyanates under these conditions.

Comparative example 3:

In a four-necked round bottom flask equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid were added to 190 g of polyisocyanate 1 (0.99 mol). The reaction lasted 10 h at 110 ° C. The system was cloudy, indicating that 4- (cyclohexylamino) -butanesulfonic acid did not react with polyisocyanates without the presence of the tertiary amine.

Comparative example 4:

In a round-bottomed flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.084 mol) of 3- (cyclohexylamino) -propanesulfonic acid, 5, were added. 4 g (0.084 mol) of dimethylcyclohexylamine to 190 g of polyisocyanate 1 (0.99 mol). The reaction lasted 10 h at 80 ° C. After cooling to room temperature, the sulfamic acid-modified polyisocyanates are obtained with the following characteristic data:

solids content: 100%

content of isocyanate groups: 19.2% by weight

average functionality of isocyanate groups: 3.4

viscosity (25 ° C): 4,600 mPa ■ s

SO3- content: 1.76% by weight

content of ethoxy units: 0

Comparative example 5:

10 g of 2-methylaminoethanesulfonic acid (0.08 mol) and 10.16 g of dimethylcyclohexylamine (0.08 mol) were used to replace the 10 g (0.042 mol) of 4- (cyclohexylamino) -butanesulfonic acid and the 5, 4 g (0.042 mol) of dimethylcyclohexylamine in example 1, the rest of the elements can be referred to example 1. The reaction mixture was heated at 100 ° C for 6 h. The system was murky. The temperature was even increased to 120 ° C, and an additional reaction time of 4 h, the system was still cloudy, indicating that 2-methylaminoethanesulfonic acid did not react with polyisocyanates and was present as crystals in the system. .

Example 19 (Application in two component aqueous coatings)

47.12 g of hydroxylacrylic resin (Antkote® 2033) with a hydroxyl number of 3.3, solids content 46%, pH 7.5-8.0, 0.6 g of wetting agent (Surfynol 104BC), 2.22g of dispersing agent (Borchi® Gen SN 95), 0.16 g of leveling agent (Baysilone Paint Additive 3468) diluted 10% with ethylene glycol butylether, 27.65 g of titanium white and 7, 06 g of deionized water and subsequently, ground to a fineness of less than 20 pm. Subsequently, 14.2 g of sulfamic acid modified polyisocyanates according to the present invention were added from said examples or comparative examples. The obtained two-component mixture was applied on different substrates and dried for 30 minutes at 80 ° C after drying on the surface. Coating films with the properties shown in Table 1 below were obtained.

The data showed that, compared to the sulfamic acid modified polyisocyanate according to Comparative Example 4, the sulfamic acid modified polyisocyanates according to other examples, by the two-stage addition process, have a longer processing time in the system. two-component coating films, and two-component coating films have better water resistance and resistance to bases.

Example 20 (Preparation of blocked modified polyisocyanates)

In a four-necked round bottom flask equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 12.5 g (0.053 mol) of 4- (cyclohexylamino) -butanesulfonic acid were added, 6.8 g (0.053 mol) of dimethylcyclohexylamine to 166 g (0.87 mol) of polyisocyanate 1. The reaction lasted 3 hours at 100 ° C. Subsequently, 71 g (0.37 mol) of polyisocyanate 1 were added and mixed homogeneously. Since the viscosity of the reaction system was relatively high, 64.7 g of N-ethyl-pyrrolidone was added to dilute the mixture at 60-70 ° C. 114 g (1.19 mol) of the 3,5-dimethylpyrazole blocking agent were added in the course of 0.5 h, until the NCO content of the system was less than 0.1% by weight, the polyisocyanates were obtained sulfamic acid modified blocked.

Under conditions of vigorous mechanical stirring, 200 g of deionized water was slowly added to the above 200 g of blocked sulfamic acid modified polyisocyanate, blue light stable white emulsions were prepared.

solids content 40% by weight

particle size (nm): 89

content of blocked isocyanate groups (based on emulsion): 5.7% by weight

viscosity (25 ° C): 210 mPa ■ s

solvent content: 6.9% by weight.

Claims (11)

1. Sulfamic acid modified polyisocyanate, which is prepared by a reaction of polyisocyanate and sulfamic acid with the formula of H T N- R: ---- SO, H wherein, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamanthyl, and 2-adamanthyl dimethyl-1-adamantyl, R2 is butyl; or R1 is one of methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, 2-dimethyl adamantyl and 3,5-dimethyl adamantyl -1-adamantyl, R2 is propyl; or R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, and 3.5-dimethyl-1, 2-dimethyl-adamantyl -adamantyl, R2 is isobutyl; preferably, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, and cycloheptyl, R2 is butyl; or R1 is methylcyclohexyl, p-methylcyclohexyl and 3,3,5-trimethylcyclohexyl, R2 is propyl; or R1 is cyclohexyl and methylcyclohexyl, R2 is isobutyl: the amount of said sulfamic acid is 0.5-20% by weight, preferably 1-10% by weight of the total weight of the polyisocyanate and sulfamic acid. 2. Polyisocyanate modified with sulfamic acid, according to claim 1, characterized in that : a) the average isocyanate functionality is at least 1.8, b) the content of isocyanate groups is 4.0-35.0% by weight, c) the SO3- content is 0.1-6.8% by weight, and optionally d) the content of ethoxy units that were attached to the polyether chain is 0-15% by weight, said polyether chain comprises an average of 5-30 ethoxy units; preferably, a) the average isocyanate functionality is 2.0-4.8, b) the content of isocyanate groups is 6.0-31.0% by weight, c) the SO3- content is 0.2-4.8% by weight, d) the content of ethoxy units that were attached to the polyether chain is 4-12% by weight, said polyether chain comprises an average of 10-20 ethoxy units. 3. Polyisocyanate modified with sulfamic acid, according to any of claims 1-2, characterized in that said polyisocyanate applied in the reaction is one or more of aliphatic, alicyclic, aromatic, araliphatic and modified polyisocyanates with an average isocyanate functionality of 2 0-5.0 and an isocyanate group content of 7.0-32.0% by weight; one or more of the aliphatic, alicyclic and modified polyisocyanates with an average isocyanate functionality of 2.0-4.0, and an isocyanate group content of 12.0-25.0% by weight are preferred; More preferred are polyisocyanates comprising isocyanurate-modified groups that are based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. 4. Process for preparing polyisocyanates modified with sulfamic acid, according to any of claims 1 -3, characterized in that said polyisocyanate reacts with sulfamic acid with the formula of Hee HN ---- R2— SO.H in the presence of tertiary amines. wherein, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamanthyl, and 2-adamanthyl dimethyl-1-adamantyl, R2 is butyl; or Ri is one of methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl adamantyl -1-adamantyl, R2 is propyl; or Ri is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3.3.5-trimethylcyclohexyl, 4-tertbutylcyclohexyl, cycloheptyl, methylcyclooctyl, 2-norcamfanyl, and 3.5-dimethyl-adamantyl -adamantyl, R2 is isobutyl; preferably, R1 is one of cyclohexyl, methylcyclohexyl, p-methylcyclohexyl, and cycloheptyl, R2 is butyl; or R1 is one of methylcyclohexyl, p-methylcyclohexyl and 3,3,5-trimethylcyclohexyl, R2 is propyl; or R1 is one of cyclohexyl and methylcyclohexyl, R2 is isobutyl; the amount of sulfamic acid is 0.5-20% by weight, preferably 1-10% by weight of the total weight of the polyisocyanate and sulfamic acid; Y wherein in said reaction, the polyisocyanates are added by a two-stage addition process, in which the first part of the polyisocyanate is mixed with the sulfamic acid, the tertiary amine and optionally the polyethers, and the reaction lasts 3-5 hours at 95-110 ° C, subsequently, the remaining part of polyisocyanate is added, after cooling to room temperature, the polyisocyanate modified with sulfamic acid is obtained; wherein the first part of the polyisocyanate represents 30-90% by weight, preferably 50-80% by weight of the total weight of the polyisocyanate. 5. Process according to claim 4, characterized in that said reaction is carried out in the presence of polyether comprising ethoxy units, and / or the polyisocyanate used already comprises ethoxypolyether units. 6. Process according to claim 4, characterized in that said polyisocyanate is one or more of aliphatic, alicyclic, aromatic, araliphatic and modified polyisocyanates with an average functionality of isocyanate groups of 2.0-5.0 and a content of groups 7.0-32.0% isocyanate by weight; one or more of the aliphatic, alicyclic and modified polyisocyanates with an average isocyanate functionality of 2.0-4.0, and an isocyanate group content of 12.0-25.0% by weight are preferred; More preferred are polyisocyanates comprising isocyanurate-modified groups that are based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. 7. Process according to claim 5, characterized in that the content of the ethoxy units attached to the polyether chain is 0-15% by weight, preferably 4-12% by weight, based on the total weight of the polyisocyanate , sulfamic acid and polyether, polyether is monohydric, the number average molecular weight is 300-1,000, preferably 400-800, the number of ethoxy units is 5-30, preferably 10-20. 8. Process according to claim 4, characterized in that said tertiary amine is a non-cyclic and / or cyclic substituted aliphatic and / or alicyclic tertiary amine; one or more of triethylamine, dimethylcyclohexylamine and N-methylmorpholine are preferred; the molar ratio of said tertiary amine to the SO3- group of sulfamic acid is 0.2-2.0: 1, the molar ratio of isocyanate groups to groups that are reactive to isocyanate groups is kept at 4-300: one; preferably, the molar ratio of said tertiary amine to the SO3- group is 0.5-1.5: 1, the molar ratio of isocyanate groups to groups that are reactive groups to isocyanate groups is kept at 6-200: one. 9. Use of the sulfamic acid-modified polyisocyanate, according to any of claims 1-3, or of the sulfamic acid-modified polyisocyanate obtained by the preparation process, according to any of claims 4-8, as a starting component in the preparation of Synthesized water dispersible polyurethane. 10. Use of the sulfamic acid-modified polyisocyanate, according to any of claims 1-3, or of the sulfamic acid-modified polyisocyanate obtained by the preparation process, according to any of claims 4-8, as a crosslinking agent in aqueous coatings of two component and water dispersible adhesives. 11. Use of the polyisocyanate modified with sulfamic acid, according to any of claims 1-3, or of the polyisocyanate modified with sulfamic acid obtained by the preparation process, according to any of claims 4-8, as a starting component in the preparation of known blocked polyurethanes in polyurethane chemistry. REFERENCES CITED IN THE DESCRIPTION This list of references cited by the applicant is solely for the convenience of the reader. They are not part of the European Patent document. Even taking into account that the compilation of the references has been done with great care, errors or omissions cannot be ruled out; EPO disclaims all liability in this regard. Patent documents cited in description • EP 0443138 A DE 2641380 A • EP 0548669 A DE 3700209 A • CN 101754990 A DE 3900053 A • DE 4433929 A DE 3928503 A • CN 1190450C EP 0336205 A • DE 1670666 A EP 0339396 A • FROM 1954093 A EP 0798299 A • FROM 2414413 TO US 2007010573 A1 • FROM 2452532 A